Solubility Parameter Components Research Articles

Polyvinyl Butyral with Different Acetalization Degrees: Synthesis and Solubility Parameters

In the research described here polyvinyl butyral (PVB) samples with mass acetalization degrees of 84.4%, 70.4%, 58.8%, 40.3% and number-average molecular weights (M n) of 29300 ∼ 36100 g mol−1 were synthesized using p-toluenesulfonic acid as a catalyst. The PVB samples were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and differential thermogravimetric analysis (DTGA). Furthermore, the solubility parameters of the PVB with different acetalization degrees were determined by the Hansen Solubility Parameter in Practice (HSPiP) software, turbidimetric titration and group contribution methods. The results showed that the total solubility parameter (δ t) and two of the solubility parameter components (polar solubility parameter δ p and hydrogen bonding solubility parameter δ h) increased linearly with the decrease of the acetalization degree of the PVB, while the change of δ d (dispersion solubility parameter) was not obvious. The correlation between the solubility parameters and acetalization degree of PVB was established. The solubility parameters obtained in this paper can be used to predict the affinity of PVB with solvents or additives, which is convenient for solvent selection and formulation design.

Pencil and Paper Estimation of Hansen Solubility Parameters.

Simple procedures to estimate Hansen solubility parameter (HSP) components from structural formulas are investigated. The best results are obtained using a simple relationship with molar volume and refractivity for the dispersion component, and using additivity models based on tailored fragments specifically designed for the polar and hydrogen bonding components. Despite large errors for some classes of chemicals, including small inorganic molecules, ionic liquids, and high halogen compounds, these models yield average absolute deviations from reference on par with state-of-the-art models and lower than reported using molecular dynamics simulations or nonlinear quantitative structure–property relationship models based on a limited set of quantum chemical descriptors. In contrast to group contribution methods that are either more restricted in scope or heavily parameterized, they are thoroughly validated and very easy to apply. Furthermore, the errors observed are easy to rationalize and may usually be anticipated. This work sheds light on some limitations inherent to pure additivity approaches for HSP prediction and provides a first step toward better models. A Python script implementing the procedure and the fully detailed results are provided as the Supporting Information.

Modified kaolinites-polyalkyl methacrylate nanocomposites: Exploring relations between solubility parameters and thermal properties forin situsolution polymerization

Poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and their nanocomposites (Kao-PMMAs and Kao-PEMAs) with various kaolinite intercalation compounds were prepared in several solution polymerization media in order to examine relations between solubility parameters of polymerization medium including monomer and solvent/solvents and of intercalating agents and thermal properties of the resultant materials. The measurements of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetry/derivative thermogravimetry, and differential scanning calorimetry were used to characterize these materials. The increase in solubility parameter of polymerization medium improved thermal decomposition temperatures of PEMA and Kao-PEMAs when it usually induced a decrease in those of PMMA and Kao-PMMAs and in glass transition temperatures of all materials. These results were also examined in respect of the effects of hydrogen bonding and dispersion components of solubility parameters of intercalating agents on the thermal properties of these materials. POLYM. COMPOS., 37:2333–2341, 2016. © 2015 Society of Plastics Engineers

Influence of matching solubility parameter of polymer matrix and CNT on electrical conductivity of CNT/rubber composite.

We report a general approach to fabricate elastomeric composites possessing high electrical conductivity for applications ranging from wireless charging interfaces to stretchable electronics. By using arbitrary nine kinds of rubbers as matrices, we experimentally demonstrate that the matching the solubility parameter of CNTs and the rubber matrix is important to achieve higher electrical conductivity in CNT/rubber composite, resulting in continuous conductive pathways leading to electrical conductivities as high as 15 S/cm with 10 vol% CNT in fluorinated rubber. Further, using thermodynamic considerations, we demonstrate an approach to mix CNTs to arbitrary rubber matrices regardless of solubility parameter of matrices by adding small amounts of fluorinated rubber as a polymeric-compatibilizer of CNTs. We thereby achieved electrical conductivities ranging from 1.2 to 13.8 S/cm (10 vol% CNTs) using nine varieties of rubber matrices differing in chemical structures and physical properties. Finally, we investigated the components of solubility parameter of CNT by using Hansen solubility parameters, these findings may useful for controlling solubility parameter of CNTs.

Synthesis of monodisperse anionic submicron polystyrene particles by stabilizer-free dispersion polymerization in alcoholic media

In this work, monodisperse polystyrene (PS) particles were synthesized in ethanol/water medium using sodium salt of styrene sulfonic acid and 2,2′-azobis(isobutyronitrile) as ionic comonomer and nonionic initiator, respectively. The polymerization was carried out at low agitation speed, and no stabilizer (or surfactant) was added to the polymerization medium. This polymerization system (stabilizer-free dispersion polymerization) was initiated as a homogeneous solution of monomer, comonomer, medium, and initiator. With the production of free radicals, polymerization developed into a heterogeneous system. The effect of various polymerization conditions on the size and size distribution of the obtained particles was evaluated. The experimental results showed that with an increase in ethanol content, the size of the particles increased while no significant change was observed in particle size distribution. Furthermore, with increasing ionic comonomer content, the size of the particles decreased and their size distribution became broader. Moreover, it was observed that addition of an electrolyte to the polymerization medium also increased the particles’ size and broadened their size distribution. It is noteworthy to point out that the coagulation occurred in higher amounts of electrolyte. Finally, it is concluded that the polar component of Hansen solubility parameter of the polymerization medium affects the particle size and particle size distribution greatly.

Estimation of Hansen solubility parameters using multivariate nonlinear QSPR modeling with COSMO screening charge density moments

New QSPR multivariate nonlinear models based on artificial neural network (ANN) were developed for the prediction of the components of the three-dimensional Hansen solubility parameters (HSPs) using COSMO-RS sigma-moments as molecular descriptors. The sigma-moments are obtained from high quality quantum chemical calculations using the continuum solvation model COSMO and a subsequent statistical decomposition of the resulting polarization charge densities. The models for HSPs were built on a training/validation data set of 128 compounds having a broad diversity of chemical characters (alkanes, alkenes, aromatics, haloalkanes, nitroalkanes, amines, amides, alcohols, ketones, ethers, esters, acids, ion-pairs: amine/acid associates, ionic liquids). The prediction power of the correlation equation models for HSPs was validated on a test set of 17 compounds with various functional groups and polarity, among them drug-like molecules, organic salts, solvents and ion-pairs. It was established that COSMO sigma-moments can be used as excellent independent variables in nonlinear structure–property relationships using ANN approaches. The resulting optimal multivariate nonlinear QSPR models involve the five basic sigma-moments having defined physical meaning and possess superior predictive ability for dispersion, polar and hydrogen bonding HSPs components, with test set correlation coefficients R 2 d = 0.85, R 2 p = 0.91, R 2 h = 0.92 and mean absolute errors of Δ δ d = 1.37 MPa 1/2, Δ δ p = 1.85 MPa 1/2 and Δ δ h = 2.58 MPa 1/2.

Determination of Hansen Solubility Parameters for the Solid Surface of Cellulose Acetate Butyrate by Inverse Gas Chromatography

The specific retention volumes, , for adsorption of 21 solute probes on the solid surface of cellulose acetate butyrate (CAB) were determined in the temperature range 343.15 to 403.15 K by inverse gas chromatography (IGC). The weight fraction activity coefficients, , and Flory–Huggins interaction parameters, , were evaluated using . Both and values decreased with increase of temperature in all the solutes. Further, the values increased with increase of chain length in n-alkanes, but in the case of alcohols the trend was reversed. values were less than 0.5 in polar solutes and greater than 0.5 in 1-alkanes and alcohols. The Hansen solubility parameters (HSP) were calculated by relating with the cohesive energy of adsorption of the solutes on the surface of CAB. The adsorption model proposed by Snyder and Karger was used to determine the HSP for the CAB. The dispersive, , polar, , and hydrogen bonding components of HSP decreased with increase of temperature and the relative error associated with these parameters increased with increase of temperature. The characterization of the solid surface of CAB in terms of the three solubility parameter components was analyzed and is discussed.

Investigation of Physical Chemistry Properties of Asphaltenes Using Solubility Parameters of Asphaltenes and Their Fractions A1 and A2

The Sphere method developed by Hansen (Hansen, C. M. Hansen Solubility Parameters: A User’s Handbook; CRC Press: Boca Raton, FL, 1999) to calculate components of solubility parameters (SP), δD, δP, and δH, where D, P, and H stand for dispersion, polar, and hydrogen bonding respectively, have been applied to resins, to asphaltenes, and fractions A1 and A2. Mean values for these compounds in MPa0.5 were asphaltenes (19.5 ± 0.1, 4.7 ± 0.2, 4.2 ± 0.1); A2 (19.6 ± 0.1, 5.8 ± 0.1, 4.4 ± 0.2); A1 (20.9 ± 0.2, 5.6 ± 0.3, 6.8 ± 0.2); resins (18.6 ± 0.2, 3.6 ± 0.3, 3.2 ± 0.3). Also, the SP components of the asphaltene sample (AsH-NS), denuded from acidic natural surfactant (NS), were determined affording values equal to A2. These values were obtained after using 57 solvents, and the method is consistent with all known solubility properties of asphaltenes and confirm the expected solubility behavior of A1 and A2, with A1 being the less soluble material in all solvent examined. Excellent affinity between asphaltene with resins was predicted as well as affinity between samples examined. These results are coherent with a colloidal model whereby fraction A1 is in not contact with the solvent, being within a core shielded from the media by a periphery composed by fraction A2 and NS. Flocculation results measured in n-C7−1-methylnaphthalene mixtures correlate with the above SP showing the following order of flocculation tendency: A1 ≫ A2 > asphaltenes (AsH). We also observed that flocculation points of A2 and AsH-NS were very close, and this strongly supports the colloidal model above. SP were helpful in analyzing other properties such as adsorption, vaporization, affinity, and molecular mass and paraffin’s properties.

Conductive Polymer nano-bioComposites (CPC): Chitosan-carbon nanoparticle a good candidate to design polar vapour sensors

Conductive Polymer nanoComposites (CPC) prepared from the dispersion of carbon nanoparticles into a chitosan biomatrix (Chit-CNP) have been successfully used to develop polar solvent vapours (water and methanol) sensors, by spray layer-by-layer process. Such CPC transducers give a quantitative response when exposed to water vapour that can be considered as a sorption isotherm and very well fitted with a Langmuir–Henry-Clustering (LHC) diffusion model. This model gives a new insight into understanding of chemo-electrical behaviour of CPC and appears to be helpful to optimise sensor design by tailoring transducer initial characteristics to suitable solvent vapour fraction measurement range. Moreover, Chit-CNP sensors selectivity allowed ranking vapours by relative response amplitude ( A r) in the following order: water > methanol > toluene. The origin of this selectivity was not found into χ 12 the Flory–Huggins polymer/solvent interaction parameter but into δ p, ɛ r and d, respectively the polar component of solubility parameter, the dielectric permitivity and the molecules size of solvents. Surprisingly little influence of chitosan nature and treatment on chemo-electrical behaviour was found.

Estimation of solubility parameter components of solutes and polymers using heat of vaporization and heat of sorption of solutes

AbstractIn a recent study, a two‐dimensional solubility parameter model was used to correlate the heat of solution for solutes ranging from n‐alkanes to alcohols, dissolved in isotatic polypropylene (PP), poly(ethyl ethylene) (PEE), and poly(dimethylsiloxane) (PDMS). When literature data of solubility parameter components of solutes were used, the correlation had some scattering for solutes with low values of cohesive energy density. In this study, the components of solubility parameters of solutes and polymers were estimated from cohesive energy and heat of sorption of solutes. Good correlation was obtained for the specific heat of sorption (ΔUsorp/V) for solutes ranging from n‐alkanes to alcohols, and PDMS had a polar component as previously estimated. Free volume effect in solution process may be the source of a small systematic deviation from the model. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Determination of Hansen solubility parameters for cellulose acrylate by inverse gas chromatography

The solubility parameters of cellulose acrylate (CEA) were examined by inverse gas chromatography (IGC). The test probes were pentane, hexane, heptane, octane, nonane, ether, acetone, tetrahydrofuran, toluene, chloroform, isopropanol, and hexanol. The minimal test probe was injected into chromatographic column in order to achieve the infinite dilution conditions. The retention times of the test probes were determined and Flory–Huggins interaction parameters (χ) and solubility parameters (δ2) were calculated according to DiPaola-Baranyi and Guillet method from experimentally collected retention data for the series of carefully selected test probes. The Hansen’s three-dimensional solubility parameters concept is applied to determine the components (δd, δp, δh) of total solubility parameter (δT). The solubility parameter (δT) was increased with increasing temperature.

Evaluation of solubility parameters for nonvolatile branched hydrocarbons by inverse gas chromatography

AbstractFlory‐Huggins interaction parameters determined by inverse gas chromatographic (IGC) technique have been used for the estimation of solubility parameters of nonvolatile branched hydrocarbon solvents. A family of isosteric branched hydrocarbons consists of one apolar stationary phase, 19,24‐dioctadecyldotetracontane (C78), and four polar stationary solvents formed by replacing one of the CH3 groups of C78 by OH (POH), CN (PCN), SH (PSH), CF3 (MTF), and two other polar solvents formed by replacing four CH3 groups of C78 with four CF3 (TTF) and OCH3 (TMO) are investigated. The three‐dimensional Hansen solubility parameters of the solvents have been estimated following the approaches of Voelkel and the method of Huang at five different temperatures. In the three components estimated by Voelkel method, the dispersion component is decreasing rapidly, whereas the polar, and hydrogen bonding components of the solubility parameters are increasing with temperature. In the components of solubility parameter estimated by Huang method, the dispersion and hydrogen bonding components are slowly decreasing with temperature, however, the polar components are almost constant with temperature. The components of solubility parameters for different solvents have been discussed in terms of solvent polarity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Inverse Gas Chromatographic Study of the Oxidation Stability of Lubricating Base Oils via Solubility Parameter Calculations

The Flory-Huggins interaction parameter (chi1, 2(infinity)) and solubility parameter (delta2) and its hydrogen bonding sensing component (delta(h)) were determined using inverse gas chromatography (IGC). These parameters were successfully used in the probes of chemical changes that occur during the oxidation of naphthenic and paraffinic base oils in a GC column. Changes in chi1, 2(infinity) values reflect the different types of intermolecular interactions (dispersive, polar, hydrogen bonding) of the given lubricating base oil during oxidation. The obtained results showed that delta(h) component of solubility parameter is the most important parameter for probing the oxidative-chemical changes during the oxidation of given lubricating oils.

The partial solubility parameters: An equation-of-state approach

The division of the well-known solubility parameter into its dispersion, polar, and hydrogen-bonding components has significantly upgraded its capacity and usefulness in the screening and selection of the appropriate solvents in Industry and in Laboratory. This work presents a new statistical thermodynamic approach for the estimation of these partial components over a broad range of temperature and pressure. Key to this approach is the development of explicit expressions for the contribution of dispersion, dipolar, and hydrogen-bonding interactions to the potential energy of the fluid. The approach is applicable to ordinary solvents, to supercritical fluids, as well as to high polymers. Information on various thermodynamic properties of fluids is used in order to estimate the three solubility parameter components. Extensive tables with the key parameters are presented. On the other hand, available information on these separate components is exploited in order to extract information for the thermodynamic behaviour of the fluids over an extended range of external conditions.

Three-dimensional solubility parameters of poly(ɛ-caprolactone)

The three-dimensional solubility parameter model was applied to analyze solution thermodynamic data of 27 solutes in poly(ε-caprolactone) (PCL) between 70 and 110 °C. A linear regression method was compared with a nonlinear least square regression method, which searches solubility parameter components by minimization of the sum of error squares. The parameters of polymers were the same by both methods. When compared with the error in predicting χRT/V, the data showed a different slope from the simple three-dimensional model. These deviations were reduced by a different model using a smaller weight on the polar and hydrogen bonding components. In the new model, the solubility parameter components were closer to the value of a structure analogue of PCL. The confidence intervals for the parameters were estimated from a linearized equation based on the sum of error squares. The solubility parameter components obtained were different from the average values of the five solutes with the smallest χ. The inclusion of solutes with high hydrogen bonding components contributed to the increase of the component in the nonlinear regression method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2002–2009, 2006

Multicomponent solubility parameters of poly(vinyl chloride) and poly(tetramethylene glycol)

The one-, two-, and three-dimensional solubility parameter models were used to analyze solution thermodynamic data of several solutes in poly(vinyl chloride) (PVC) and poly(tetramethylene glycol) (polytetrahydrofuran, PTHF). A previous proposed method to estimate solubility parameter, based on direct minimization of the sum of the squares of errors in the prediction of χRT/ V, was extended to two- and three-dimensional, and the results of solubility parameter components were the same as the linear regression method. The one-dimensional model gave the smallest sum of the squares of errors, followed by the three-dimensional model, then the two-dimensional model. A systematic error was identified when two- and three-dimensional models were used for the data. A method using less weight on polar and hydrogen-bonding components produced smaller errors for the two- and three-dimensional models.

The algorithmic calculations of solubility parameter for the determination of interactions in dextran/certain polar solvent systems

The dextran/solvent system was employed for the evaluation of the parameters and various molecular contributions on the basis of solubility parameter with regard to the theoretical methods of Hoy and Van Krevelen–Hoftyzer pair. The theoretical magnitudes correlated quite well with the experimental values determined previously for the same system. The Δ δ value predicted as ⩽5 for various systems previously, appeared to be >5 for the dextran/solvent systems obtained from the diagrams plotted using several solubility parameter components. An order with respect to the solvent has been proposed with regard to the distance of the solubility parameter components of the solvent from the center of the circle for which, water does not seem to be a good solvent for the system under study since it remains outside the circle of those diagrams.

Evaluation of solubility parameters during polymerisation of amine-cured epoxy resins

A new procedure for the calculation of solubility parameter evolution during polymerisation has been developed for amine-cured epoxy systems, which allows quantitative thermodynamic modelling of chemically induced phase separation (CIPS). Solubility parameters calculation, chemical analysis based on near infrared spectroscopy and curing kinetics results obtained by differential scanning calorimetry will allow to model the evolution of the Flory–Huggins interaction parameter in amine-cured epoxy blends. The resin system investigated was based on a diglycidyl ether bisphenol A (DGEBA) epoxy resin cured with isophorone diamine (IPD) blended with various reactive epoxydised dendritic hyperbranched polymer modifiers (HBP), yielding a CIPS-controlled morphology. The analysis showed the evolution of the different contributions to the solubility parameters to follow the polymerisation kinetics. The dispersive contribution had the highest value at all stages of polymerisation, but the hydrogen and polar contributions showed the largest variation. By evaluating the dynamic evolution of the solubility parameter components, the Flory–Huggins interaction parameter in the epoxy resin-hyperbranched polymer blends has been modelled as a function of time. This procedure, combined with thermodynamic modelling, will enable to predict phase diagrams in CIPS thermosetting blends quantitatively.

Polygon Mapping with Two-Dimensional Solubility Parameters

In the selection of liquids and liquid mixtures to dissolve a given material, the two-dimensional solubility parameter is shown to be both easier to use and much more accurate than the commonly used three-dimensional solubility parameter. The solubility parameter of each liquid is represented as a vector with complexing and field force components. The complexing solubility parameter component characterizes the ability of a liquid to form interactions that require a specific orientation between molecules while the field force solubility parameter component includes dipole interactions, which usually are only significant for associated liquids, like alcohols, and dispersion interactions. On the basis of five postulates, the solvent power of each liquid is represented by a point in two-dimensional solubility parameter space while the set of solvents for a given material are represented by the area of a polygon. The assignment of solubility parameter components for 50 liquids were made on the basis of their ability or inability to dissolve 35 polymers and 3 dyes in the study and 33 polymers from a previous study and resulted in a 99.5% accuracy of the placement of nonsolvents outside and of solvents inside the solubility areas. These solubility areas enabled the correct prediction of over 100 solvents formed from mixtures of liquids that individually are nonsolvents. Finally, as an example, the two-dimensional solubility parameter was applied to the selection of solvents for forming colored, spherical polymer particles, encapsulated in clear polymer shells by spray drying

Analysis of PVC blends by three‐dimensional solubility parameters

AbstractAn investigation was undertaken on the application of the three‐dimensional solubility parameter method to predict miscibility of polyblends. The three‐dimensional method attempts to account for the combined effects of dispersion, polar, and hydrogen bonding interactions between molecules. This study focused mainly on the miscibility of blends of poly(vinyl chloride) (PVC) with homopolymers as well as with copolymers. The three components of solubility parameters were calculated from the group contributions of the structural units of the polymers. By comparing the parameters of different PVC blends in two categories, PVC/homopolymer and PVC/copolymer blends, the miscibility trend of PVC blends was revealed. The three‐dimensional solubility parameter approach successfully predicted the miscibility of several homopolymers. For copolymers, the chance of miscibility was increased because of the ability to adjust the solubility parameter through composition. This was reflected in a smaller distance between the solubility parameter of copolymer and that of PVC. Experimental results reported in the literature confirmed this conclusion. © 1993 John Wiley & Sons, Inc.